Structural Elucidation in Organic Chemistry

Topic 10.3 : Structural Elucidation in Organic Chemistry 1. HCI/2009/P3/Q3e

2.

DHS/2009/P3/Q2b The carbon to hydrogen ratio of P is 1 : 2. P does not contain benzene ring, but could contain alkene group. P undergoes electrophilic and R in unequal proportion. addition with hydrogen chloride gas to form Q

P is an unsymmetrical alkene. Q and R are halogenoalkanes. Q and R undergo nucleophilic substitution with sodium hydroxide to form S and T respectively. S and T are alcohols. S is not oxidized by acidified potassium manganate (VII). S is a tertiary alcohol. T is oxidized by acidified potassium manganate (VII) to form U. T is a primary or secondary alcohol. U could be ketone. carboxylic acid or

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U undergoes neutralisation / acid base reaction with sodium carbonate to liberate carbon dioxide gas. U is a carboxylic acid, hence T is a primary alcohol. P undergoes (strong) oxidation with acidified potassium manganate (VII) to form V, C5H10O, which has only one oxygen atom, and carbon dioxide. P has a terminal alkene group. V is a ketone. V undergoes condensation with orange precipitate. V is a ketone / carbonyl compound. V undergoes reduction with does not exhibit optical activity. lithium 2,4-dinitrophenylhydrazine to form an

aluminium

hydride

to

form

W,

which

W is a secondary alcohol and is a symmetrical molecule.

H C H C

CH2CH3 CH2CH3

H H C H

CH2CH3 C Cl

H Cl C H

CH2CH3 C H

CH2CH3
Q

CH2CH3
R

H H C H

CH2CH3 C OH HO

H C H

CH2CH3 C H HO

O C

CH2CH3 C H

CH2CH3
S

CH2CH3
T U

CH2CH3

CH2CH3 O C CH2CH3
V

CH2CH3 HO C H

CH2CH3
W

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3.

IJC/2009/P3/Q1f

4.

ACJC/2009/P2/Q4b

5.

JJC/2009/P2/Q6c

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(ii) Excess NH3, heat under reflux in ethanol 6. MJC/2009/P3/Q4c

7.

NJC/2009/P3/Q2e

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8.

NYJC/2009/P3/Q5c STRUCTURES

H3C C CH

OH CH CH CH CH3

[1]

M is

CH3 C
O

[1]

N is

O Na C
O

[1]

R is O HO C C C O O OH

[1]

P is

HO C [1] Q is O CH3

EXPLANATION OF THE REACTIONS DESCRIBED

[1] M decolourises aqueous bromine due to electrophilic addition across the alkene (C=C) functional group. [1] M produces white fumes (of HCl) with PCl5 due to a substitution reaction of the (secondary) alcohol functional group.

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[1] M produced 3 compounds, N, P and Q with hot acidified potassium manganate (VII) due to oxidative cleavage of the (2) alkene functional groups present. [1] N does not undergo mild oxidation with Fehlings reagent as it is not an aldehyde.

[1] N gives a yellow ppt (of CHI3) and salt R with aq alkaline iodine due to the (mild) oxidation (and cleavage) of the CH3COR group. [1] P gives an effervescence (of CO2 ) with Na2CO3(s) due to a neutralization reaction with the carboxylic acid functional group. [1] P gives an orange precipitate with 2,4-DNPH due to condensation with the ketone functional group. [1] Q gives an effervescence (of CO2 ) with Na2CO3(s) due to a neutralization reaction with the carboxylic acid functional group. [1] Q does not give an orange precipitate with 2,4-DNPH due to the absence of a carbonyl functional group for condensation. RJC/2009/P2/Q4(a),(b)
(a) (b) Structural/positional isomerism Geometric isomerism

9.

H C C HO OCH3 cis

H CH3

HO CH3O H trans H C C CH3

10.

SAJC/2009/P3/Q4c Information Stereoisomer A Deduction - contains either an alkene with nonidentical groups on the same carbon or chiral carbon

A reacts with hot acidified potassium - A undergoes oxidation manganate(VII) solution - A contains C=C

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B forms a yellow precipitate with hot - B contains CH3COalkaline iodine solution. (do not accept CH3CHOH-)

Cold alkaline hydrogen cyanide was - B is a ketone which undergoes added to B and the mixture was nucleophilic addition with HCN reduced to form compound C - C contains an amine functional group

Compound D formed white precipitate with ethanolic silver nitrate solution.

- D contains chloroalkane which forms AgCl

Compound D was reacted with phosphorous pentachloride to form compound E.

- D is an alcohol or carboxylic acid (do not accept D contains OH group) which undergoes nucleophilic substitution / displacement reaction to form E which is a an acid chloride.

Compounds C and E were then reacted - condensation reaction took place to form two compounds F and G, with identical C7H14O2NCl. Compound F is neutral. - F is an amide or F does not contain phenol/carboxylic acid/amine. Compound A Structure Compound D
CH2Cl C HO O

molecular

formula

Structure

CH2Cl H

CH2CH3 CH3

B
O C

CH2CH3 CH3

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CH2CH3 HO C CH2NH2

F
HO

CH2CH3 C CH2NHCOCH2Cl

CH3

CH3
G
CH2CH3 CH2ClCOO C CH2NH2

CH3

11.

SAJC/2009/P3/Q5c Information Deduction

Both A and B do not react with - A and B do not have COOH Na2CO3

A and B do not give positive test

A and B do not contain any methyl

ketone CH3CO- or CH3CHOH- group

0.370 g of A reacts with sodium to Flammable gas H2 form a flammable gas that takes up No of moles of A = 0.370/74 = 0.005 125.8 cm3 of space at 32.5 oC and 101 mol kPa. 101000 x 125.8 x 10-6 =n x 8.31 x (273+32.5) No of moles of H2 = 0.005 mol - mole ratio of A : H2 = 1 :1 - A contains 2 alcohol groups

B does not react with Na

- B does not containOH group.

* Alternatively, students can give equations to illustrate the reactions undergone by A and B

Structure A B

Structure

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Structural Elucidation in Organic Chemistry

or

or any structure with two OH groups (not CH3CHOH-) and C=C.

*[not stable]

12.

SRJC/2009/P3/Q3e

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13.

TJC/2009/P3/Q1b
High C:H ratio infers that P is an aromatic compound.

2+

P
With anhydrous aluminium chloride P undergoes electrophilic substitution reaction to form Q. As the OH is an activating group, the substituent will be directed to the ortho or para position.

2+

2+
CH2CH=CH2

OR

&+ &+ &+

P undergoes electrophilic substituition as it decolourises aqueous bromine to form white ppt R. R is 2,4,6-tribromophenol as -OH is a highly activating group.

Q react with aqueous bromine to form white ppt S, with the same no of bromine atoms per molecule of R. As Q has a C-C double bond, electrophilic addition takes place as well. This implies that 1 Br will be attached to one of the carbons of the C-C double bonds. Thus, only 2 Br will be attached directly to the benzene. S
 

( )CH2Br

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S is optically active because of its chiral carbon. The mirror image of S is nonsuperimposable. 14.

TPJC/2009/P3/Q1d
Br HO O O OH Br Br

A B C D Br E (i) A undergoes electrophilic addition with HBr to form D and E. A undergoes vigorous oxidation / oxidative cleavage with hot acidified KMnO4 to form C. C can undergo neutralization or acid-base reaction with aqueous Na2CO3 to liberate CO2 gas. B undergoes vigorous oxidation / oxidative cleavage with hot acidified KMnO4 to form CO2 B undergoes electrophilic addition with HBr followed by nucleophilic substitution with aqueous NaOH to form hexan-2,3,5-triol. (ii) A cannot form cis-trans isomers as it is a cyclic alkene and the trans isomer will result in bond angle strain. B can form a pair of cis-trans isomers as it has an C=C bond with each carbon bonded to two different groups of atoms.

H H trans

cis

hexan-2,3,5-triol has 3 chiral carbons, hence no. of optical isomers = 23 = 8

YJC/2009/P3/Q5c 15.

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Structural Elucidation in Organic Chemistry

ACJC/2009/P3/Q4b 16. A has amine group being basic. No reaction with aq Br2 shows absence of
phenylamine. A is a ketone. . A has a benzene ring , and is 2,4 directing. A undergoes nucleophilic substitution with aq OH- forming C. C has a primary alcohol forming COOH confirming by reaction with carbonate. A undergoes elimination .
A
CH2Cl
COCH2Cl CH2NH2

NO2 N N H NO2

CO

CH2NH2

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C
CH2OH CO CH2NH2 CH2OH CO

CH2NH2

E
CH2 H N C O

IJC/2009/P3/Q3a 17. (i)

(ii)

IJC/2009/P3/Q5d 18.

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Structural Elucidation in Organic Chemistry

SRJC/2009/P3/Q3e 19. Cl Cl

CH3 C H

C CH2Cl CH3
A

OH OH CH3 C H
CHI3

C CH2OH CH3
B C

O Na O
+-

OH C C CH2OH CH3 OH
D

HOOC

C COOH CH3
E

NYJC/2009/P3/Q5c 20.
STRUCTURES

H3C C CH

OH CH CH CH CH3

[1]

M is

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Structural Elucidation in Organic Chemistry

CH3 C
O

[1]

N is

O Na C
O

[1]

R is O HO C C C O C CH3 O HO O OH

[1]

P is

[1]

Q is

EXPLANATION OF THE REACTIONS DESCRIBED [1] M decolourises aqueous bromine due to electrophilic addition across the alkene (C=C) functional group. [1] M produces white fumes (of HCl) with PCl5 due to a substitution reaction of the (secondary) alcohol functional group. [1] M produced 3 compounds, N, P and Q with hot acidified potassium manganate (VII) due to oxidative cleavage of the (2) alkene functional groups present. [1] N does not undergo mild oxidation with Fehlings reagent as it is not an aldehyde.

[1] N gives a yellow ppt (of CHI3) and salt R with aq alkaline iodine due to the (mild) oxidation (and cleavage) of the CH3COR group. [1] P gives an effervescence (of CO2 ) with Na2CO3(s) due to a neutralization reaction with the carboxylic acid functional group. [1] P gives an orange precipitate with 2,4-DNPH due to condensation with the ketone functional group. [1] Q gives an effervescence (of CO2 ) with Na2CO3(s) due to a neutralization reaction with the carboxylic acid functional group.
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Structural Elucidation in Organic Chemistry

[1]Q does not give an orange precipitate with 2,4-DNPH due to the absence of a carbonyl functional group for condensation.

RI/2009/P3/Q1c-e 21. (c)

Compound D is
    

      

D does not contain OH nor COOH since it does not react with sodium. It is a diester formed when OH and COOH groups of one lactic acid molecule reacts with the COOH and OH groups respectively of another lactic acid molecule. (d)(i) E has a chiral centre as it rotates planepolarised light. E is an aldehyde since it reacts with Fehlings solution to give a reddish brown precipitate. 0.24 0.01 = 1 mol Amount of hydrogen evolved with sodium per mol of E = 24 Hence two displaceable H are present there are two OH group.

E is

 

       

 

(ii)

E is an alcohol. The stability of its anion is lower than the stability of the anion of lactic acid as the anion is destabilised by the electrondonating CH2CH(OH)CHO group. Lactic acid is a much stronger acid as its anion forms two equivalent resonance structures with the negative charge on O delocalised over two electronegative O atoms.
           

(e)(i)

maleic acid (ii)

fumaric acid

Intramolecular hydrogenbonding occurs in maleic acid and thus it has lower melting point as there are less sites for intermolecular hydrogen bonding. + + & & 239 2 & & 2 2 2 +

Structural Elucidation in Organic Chemistry

intramolecular hydrogen bond +

RI/2009/P3/Q5b 22.
(b) Information Formula of G = C8H11O3N Deduction of structure Index of unsaturation = ( 2x8+211+1) = 4 (or high C to H ratio)

G is likely to contain a benzene ring/ aromatic.

G rotates planepolarised light. G is likely to contain at least one chiral carbon.

G gives a violet colouration with G is a phenol with violet colourtion formed by neutral FeCl3 solution complex formation. OH via acid-base reaction. G is insoluble in water but G is likely to contain an amine group, with NH2 dissolves in dil H2SO4. being protonated by H+.

G reacts with 2 mol of aq NaOH There are 2 phenolicOH group in G, reacting with

G is oxidised by K2Cr2O7 to G is a secondary alcohol and is oxidised to a form a product which reacts ketone by K2Cr2O7. with 2,4DNPH to give an orange ppt. H is formed by reaction of G H is formed from G by dehydration, it is likely an with Al2O3 C8H7O3NBr4. alkene.

H reacts with aq Br2 to form The product is likely to be a bromohydrin formed by electrophilic addition and electrophilic substitution into activated benzene ring. G reacts with ClCOCOCl to The phenol, secondary alcohol and amine reacts

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Structural Elucidation in Organic Chemistry

form J which has 3 hexagonal with ClCOCOCl via nucleophilic substitution. rings. 3 hexagonal ring cyclic esters and amides formed with the phenolic OHs and alcoholicOH and amine on adjacent carbon atoms.

SRJC/2009/P3/Q5a 23. (a)

G undergoes oxidation with acidified KMnO4. H undergoes nucleophilic substitution with PCl5. o H is an alcohol or carboxylic acid o J is a halogenoalkane or acyl chloride J undergoes reduction with tin in concentrated hydrochloric acid. o J contains nitrobenzene o K contains phenylamine K reacts with (C2H5)2NCH2CH2OH through esterification/nucleophilic substitution/acylation o J must contain acyl chloride o H is a carboxylic acid

H2 N
K is

COCl or

H 2N

COOH

NO2 J is

COCl

NO2 H is

COOH
H

O NO2 C H

NO2

CH3

NO2

C OH H

G is (7 out of 8 marks)

or

or

TPJC/2009/P3/Q4b 24.

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Structural Elucidation in Organic Chemistry

TPJC/2009/P3/Q5c 25.

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Structural Elucidation in Organic Chemistry

CH3 HO CH2C O
G

CH3 HO Br CH2C O H

H
COOH HO COOH

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Structural Elucidation in Organic Chemistry

CH3 HO CH2CHO

2 Cu

2+

5 OH-

CH3 -O CH2COO-

Cu2O

3 H 2O

CH3 HO CH2CHO

7O

COOH HO COOH

CO2

2 H 2O

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